Polymers prepared from mevalonolactone and derivatives

文档序号：526157 发布日期：2021-06-01 浏览：27次中文

阅读说明：本技术 由甲羟戊酸内酯和衍生物制备的聚合物 (Polymers prepared from mevalonolactone and derivatives ) 是由 D·杜加尔 T·弗莱德伯格于 2015-11-12 设计创作，主要内容包括：本申请涉及由甲羟戊酸内酯和衍生物制备的聚合物。本文描述了衍生自生物基化合物、并且尤其是生物基甲羟戊酸内酯和其相关衍生物的聚合物前驱体化合物(也称为聚合物构筑嵌段)。通过氧化,这些生物基前驱体可以反应产生用于(不饱和)聚酯、聚酯多元醇和聚酰胺的构筑嵌段,以及用于缩水甘油酯和ω-烯基酯的前驱体。通过还原,这些生物基前驱体可以反应产生用于(不饱和)聚酯、聚酯多元醇、聚碳酸酯的构筑嵌段,以及用于缩水甘油醚和ω-烯基醚的前驱体。通过亲核开环和/或酰胺化,这些生物基前驱体可以反应产生用于聚酯多元醇、用于聚氨基甲酸酯的增链剂或聚酯-酰胺的构筑嵌段。(The present application relates to polymers prepared from mevalonolactone and derivatives. Described herein are polymer precursor compounds (also referred to as polymer building blocks) derived from biobased compounds, and in particular biobased mevalonolactone and related derivatives thereof. By oxidation, these biobased precursors can react to produce building blocks for (unsaturated) polyesters, polyester polyols and polyamides, as well as precursors for glycidyl esters and omega-alkenyl esters. By reduction, these bio-based precursors can react to produce building blocks for (unsaturated) polyesters, polyester polyols, polycarbonates, and precursors for glycidyl ethers and omega-alkenyl ethers. These biobased precursors can react to produce building blocks for polyester polyols, chain extenders for polyurethanes, or polyester-amides through nucleophilic ring opening and/or amidation.)

1. A biobased polymer precursor compound of a mevalonolactone-diol or mevalonolactone-diacid or derivative thereof, selected from the group consisting of formula (XXVa), formula (XXVb), formula (XXVc), formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof:

wherein, independently at each occurrence:

each R₁Is H or alkyl; and is

Each R₂Is an alkyl group.

2. The compound of claim 1, wherein each R₂Is selected from C₁-C₆An alkyl group.

3. The compound of claim 1, wherein the compound is selected from the group consisting of formula (XXVb), formula (XXVc), formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof.

4. The compound of claim 1, wherein the compound is selected from the group consisting of formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof.

5. The compound of claim 1, wherein the compound is selected from the group consisting of formula (XXVa), formula (XXVb), formula (XXVc), and combinations thereof.

6. The compound of claim 1, wherein the compound is formula (XXVb).

7. The compound of claim 1, wherein the compound is of formula (XXVc).

8. The compound of claim 1, wherein the compound is of formula (XXVd).

9. The compound of claim 1, wherein the compound is of formula (XXVe).

10. The compound of claim 1, wherein the compound is of formula (XXVf).

11. A biobased polymer comprising repeating monomer units synthesized from a biobased polymer precursor compound of a mevalonolactone-diol or mevalonolactone-diacid or derivative thereof selected from the group consisting of formula (XXVa), formula (XXVb), formula (XXVc), formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof:

wherein, independently at each occurrence:

each R₁Is H or alkyl; and is

Each R₂Is an alkyl group.

12. The compound of claim 11, wherein each R₂Is selected from C₁-C₆An alkyl group.

13. The compound of claim 11, wherein the compound is selected from the group consisting of formula (XXVb), formula (XXVc), formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof.

14. The compound of claim 11, wherein the compound is selected from the group consisting of formula (XXVd), formula (XXVe), formula (XXVf), and combinations thereof.

15. The compound of claim 11, wherein the compound is selected from the group consisting of formula (XXVa), formula (XXVb), formula (XXVc), and combinations thereof.

16. The compound of claim 11, wherein the compound is formula (XXVb).

17. The compound of claim 11, wherein the compound is of formula (XXVc).

18. The compound of claim 11, wherein the compound is of formula (XXVd).

19. The compound of claim 11, wherein the compound is of formula (XXVe).

20. The compound of claim 11, wherein the compound is of formula (XXVf).

Technical Field

The present application relates to polymers prepared from mevalonolactone and derivatives. .

Background

Many existing chemical products, such as surfactants, plasticizers, solvents, and polymers, are currently made from non-renewable, expensive, petroleum-derived or natural gas-derived feedstock materials. The high cost of raw materials and uncertainty of future supplies require the discovery and development of surfactants, plasticizers, solvents, polymers, and thermosets that can be made from readily available, inexpensive, and renewable compounds.

Lactones are an important class of compounds that can be biochemically derived from biomass and can serve as intermediates for the sustained production of hydrocarbon biofuels and other products. In particular, mevalonolactone may be derived from biomass fermentation, producing various intermediates. Mevalonolactone (MVL) and its related derivatives, such as 2, 3-dehydromevalonolactone (4-methyl-5, 6-dihydro-2H-pyran-2-one; also known as dehydromevalonolactone, AML), represent a potentially abundant starting material which can be prepared on an industrial scale.

Mevalonate, mevalonate and mevalonolactone are present in an equilibrium which is pH dependent. Thus, a solution containing "mevalonate" may actually contain mevalonic acid, mevalonate and/or mevalonolactone. For convenience, mevalonolactone or "MVL" will be used herein inclusively. In addition, depending on the pH, the components may be in the form of salts. Depending on the reagent selected, the counter ion may be an ammonium, sodium, lithium, potassium, magnesium, calcium, aluminum, or cesium cation. The biobased mevalonolactone can subsequently be converted into a variety of useful compounds. Exemplary processes are known in the literature, with preferred processes described in the same co-pending application as US S/N62/084,689, which is incorporated herein by reference in its entirety.

Disclosure of Invention

The production of bio-based by fermentation allows MVLs to be produced in high yield and at competitive cost from low-volatility renewable feedstocks such as sugar, glycerol, syngas, or methane. Chemical products produced from bio-based MVLs and their related derivatives can meet the demand for inexpensive renewable consumer and industrial products that are not based on petroleum or other non-renewable resources. The present invention relates to industrially relevant compounds and polymers derived from bio-based MVLs and derivatives.

In one aspect, the present invention relates to polymer precursor compounds (also referred to as polymer building blocks) of bio-based MVLs or MVL derivatives. In one or more embodiments, polymer precursor compounds of ring-opened bio-based MVLs or derivatives thereof are disclosed, wherein such compounds are selected from the group consisting of: formula (XXIVa), formula (XXIVb), formula (XXIVc), formula (XXIVd), formula (XXIVe), formula (XXIVf) and combinations thereof:

wherein, independently at each occurrence,

n is 1 to 50;

m is 1 to 50;

R₁independently selected from-H or alkyl (preferably C)₁-C₆Alkyl, more preferably-CH₃) Wherein R is₁Most preferably-H;

R₂is alkyl (preferably C)₁-C₆More preferably-CH₃)；

Y may be independently selected from-O-, -S-, -N (H), or-N (R)₃)；

R₃Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group; and is

Q is a monoatomic or polyatomic linkage independently selected from: hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, aryl, substituted aryl, heteroatom-containing aryl, and substituted heteroatom-containing aryl.

The present invention also relates to polymers prepared from one or more of the above ring-opening bio-based MVL precursor compounds.

The present invention also relates to compositions comprising one or more of the ring-opened bio-based MVL compounds or polymers thereof dispersed or dissolved in a solvent system.

In one or more embodiments, polymer precursor compounds of bio-based MVL-diols or MVL-diacids are disclosed, wherein such compounds are selected from the group consisting of: formula (XXVa), formula (XXvb), formula (XXVc), formula (XXVd), formula (XXve), formula (XXvf), and combinations thereof:

wherein, independently at each occurrence:

R₁independently selected from-H or alkyl (preferably C)₁-C₆Alkyl, more preferably-CH₃) Wherein R is₁Most preferably-H; and is

R₂Is alkyl (preferably C)₁-C₆More preferably-CH₃)。

The present invention also relates to polymers prepared from one or more of the above bio-based MVL-diol or MVL-diacid precursor compounds.

The present invention also relates to compositions comprising one or more of bio-based MVL-diol or MVL-diacid precursor compounds or polymers thereof dispersed or dissolved in a solvent system.

In one or more embodiments, disclosed are polymer precursor compounds of bio-based MVL-glycidyl ethers/esters, wherein such compounds are selected from the group consisting of: formula (XVa), formula (XVb), formula (XVc), formula (XVd), formula (XVe), formula (XVf), formula (XVg), formula (XVh), formula (XVi), formula (XVj), formula (XVk), formula (XVl), formula (XVm), formula (XVn), formula (XVo) and combinations thereof:

wherein, independently at each occurrence,

R₁independently selected from-H or alkyl (preferably C)₁-C₆Alkyl, more preferably-CH₃) Wherein R is₁Most preferably-H;

R₂is alkyl (preferably C)₁-C₆More preferably-CH₃)；

y is-O-, -S-, -N (H) or-N (R)₃) (ii) a And is

R₃Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group.

The present invention also relates to polymers prepared from one or more of the above bio-based MVL-glycidyl ether precursor compounds.

The present invention also relates to compositions comprising one or more of the bio-based MVL-glycidyl ether precursor compounds or polymers thereof dispersed or dissolved in a solvent system.

The present invention also relates to various other biobased polymers and oligomers prepared from biobased MVLs or derivatives as described herein and demonstrated in the examples.

Drawings

Figure 1 shows a reaction scheme for the conversion of biobased mevalonate into various classes of compounds.

Detailed Description

In more detail, compounds (e.g., monomers, oligomers, and/or polymers) derived from bio-based compounds, and in particular bio-based MVLs and their related derivatives, are described herein. Figure 1 provides an overview of the general conversion pathway of biobased mevalonate to various classes of compounds. By oxidation, these biobased precursors can react to produce building blocks for (unsaturated) polyesters, polyester polyols, and polyamides, as well as precursors for glycidyl esters and omega-alkenyl esters (e.g., allyl ethers, homoallyl ethers, vinyl ethers, etc.). By reduction, these bio-based precursors can be reacted to produce building blocks for (unsaturated) polyesters, polyester polyols, polycarbonates, and precursors for glycidyl ethers and omega-alkenyl ethers. These biobased precursors can be reacted to produce building blocks for polyester polyols, chain extenders for polyurethanes, or polyesters by nucleophilic ring opening and/or amidation. Thus, the resulting compounds have a bio-based origin, providing several advantages over petroleum-derived chemicals and compounds.

The term "biobased" as used herein means the synthesis of compounds from biological precursors, and in particular renewable biological carbon sources such as biomass (as opposed to non-renewable petroleum-based carbon sources). ASTM sets forth the method criteria for calculating the amount of biobased material included in a composition: ASTM D6866-standard test method for determination of bio-based content of solid, liquid and gas samples using radioactive carbon analysis. The biobased content of the composition is the amount of biobased carbon in the material expressed as a weight (mass) fraction or weight (mass) percentage of total organic carbon in the material. ASTM D6866 is similar to radiocarbon dating without the age equation. It is performed by determining the ratio of the amount of radioactive carbon (14C) in the material to the amount of radioactive carbon (14C) of a modern reference standard. This ratio is reported in percent, which is referred to as the modern carbon percentage (unit "pMC"). If the material being analyzed is a mixture of today's radioactive and fossil carbon (i.e., without radioactive carbon), the pMC value obtained is directly related to the amount of bio-based material present in the sample.

ASTM D6866 distinguishes carbon produced from contemporary biomass-based input materials from carbon derived from fossil-based materials. Biomass contains a well characterized amount of carbon-14, which is readily distinguishable from other materials such as fossil fuels that do not contain any carbon-14. "biomass" is generally defined as plant material, vegetation or agricultural waste used as a fuel or energy source. Carbon-14 isotope to carbon-12 isotope ratios for biomass carbon to the artIs generally known to those of ordinary skill in the art, this ratio is about 2 x 10, based on the current natural abundance of carbon-14 relative to carbon-12 taken from an air sample^-12:1. Because the amount of carbon-14 in the biomass is known, the percentage of renewable source carbon can be easily calculated from the total organic carbon of the sample. 0% carbon-14 indicates a complete lack of carbon-14 atoms in the material, indicating a fossil or petroleum based carbon source. Similarly, 100% carbon-14 (after atmospheric correction) indicates a modern bio-based carbon source.

A modern reference standard used in the dating of radioactive carbon is the NIST (national institute of standards and technology) standard, in which the known radioactive carbon content is roughly equivalent to the notary 1950. The notary 1950 was chosen because it represented the time before the thermonuclear weapons test, which introduced large amounts of excess radioactive carbon into the atmosphere with each explosion (called a "carbon bomb"). This is a logical point in time that archaeologists and geologists use for their reference. For reference, an archaeologist or geologist uses a radioactive carbon date, with a notary 1950 equaling "zero year of age". It also represents 100 pMC. In 1963, atmospheric "carbon bombs" reached almost twice the normal level during the test peak and before discontinuing the treaty on the test. It has been roughly estimated that its distribution in the atmosphere since its emergence shows values of more than 100pMC for plants and animals living from the official 1950 to the present. Over time it gradually decreased, now approaching a value of 105 pMC. This means that fresh biomass material such as corn, sugar cane or soy will provide a radioactive carbon signature close to 105 pMC. By assuming that about 105pMC represents a biomass material today and 0pMC represents a petroleum derivative, the pMC value measured for that material will reflect the ratio of the two component types. By way of example, 100% of the material derived from today's soybeans will provide a radioactive carbon signature close to 105 pMC. But if it is diluted with 50% petroleum carbon it will provide a radioactive carbon signature close to 53 pMC.

The "biobased content" of a material is reported as a percentage value of total renewable organic carbon to total organic carbon in relation. The final result was calculated by multiplying the pMC value measured for the material by 0.95 (adjusting for carbon bomb effect). The final% value is considered the average biobased result and it is assumed that all components within the analyzed material are still alive today (over the last decade) or derived from fossil. In one aspect, the material (e.g., precursor compound or resulting polymer) used in the present invention has a biobased content of greater than 0%, more preferably greater than 10%, more preferably greater than 25%, more preferably greater than 50%, and even more preferably greater than 75%. Preferably, the materials used in the present invention are substantially entirely bio-based, meaning that they have a 95% or higher percentage of biological origin, according to ASTM D6866. Thus, it should be appreciated that bio-based products can be distinguished from petroleum-based products by carbon fingerprinting. Thus, the bio-based polymers and polymer precursors according to the invention will have a higher radioactive carbon-14 (14C) content or 14C/12C ratio than the same type of petroleum (non-renewable) derived polymers. In one aspect, the bio-based polymer precursor and/or the resulting polymer will have a 14C/12C ratio of greater than 0, preferably greater than 1.

Bio-based MVLs can serve as common starting materials for the production of several classes of polymers.

MVL and AML are themselves monomers used in polymerization reactions. The lactone structures of MVL and AML allow ring-opening co-polymerization. The ring-opening copolymerization of MVL-derived β -methyl- δ -valerolactone has been previously reported. In addition to ring opening polymerization, AML can also be a comonomer for free radical polymerization. During the dehydration reaction of MVLs, different AML isomers can be obtained, which differ by the position of unsaturation, i.e. 3, 4-dehydromevalonolactone (4-methyl-3, 6-dihydro-2H-pyran-2-one), 4, 5-dehydromevalonolactone (4-methyl-3, 4-dihydro-2H-pyran-2-one) and exo-dehydromevalonolactone (4-methylenetetrahydro-2H-pyran-2-one). These isomers can be used as ring-opening and self-assembled monomers, similar to AML.

In addition to direct polymerization of MVLs and related compounds described above, they can also be converted into building blocks for the step-wise formation of polymers, such as, inter alia, diols and diacids. These conversions can be broadly classified by the type of chemical reaction: i) oxidation, ii) reduction, iii) lactone ring opening, iv) olefin modification, and v) alcohol modification.

Sufficient oxidation of MVL and related lactones to give alpha, omega-dicarboxylic acids can be achieved by treatment with higher valent metal oxides, such as CrO, among others₆Or KMnO₄They may also be employed in catalytic amounts in the presence of a stoichiometric amount of a strong oxidizing agent. It is also possible to oxidize primary alcohols to carboxylic acids using nitric acid or molecular oxygen as the oxidizing agent. Examples of the above reagents for the oxidation of carboxylic acids as well as lactones can be found. MVL-derived dicarboxylic acids can be used as building blocks for polyesters, alkyds, unsaturated polyester resins, polyester polyols, or polyamides, to name a few.

Sufficient reduction of MVL and related lactones yields substituted α, ω -diols. The lactone functionality can be reduced to two primary alcohols using a metal hydride such as lithium aluminum hydride, elemental sodium or hydrogen in the presence of a metal catalyst. These MVL-derived diols and polyols can be used, inter alia, as building blocks for polyesters, alkyds, unsaturated polyester resins, polyester polyols, polycarbonates or vinyl-polyurethane resins.

Nucleophiles such as alcohols, thiols, or amines are capable of ring opening lactones. The reaction of MVLs and related lactones with difunctional or multifunctional nucleophiles results in the formation of substituted ring-opened MVL-based diols or polyols. The nucleophile may be homofunctional, such as glycerol or ethylenediamine, among others; or heterofunctional, such as ethanolamine or mercaptoethanol, among others. The use of these ring-opened derivatives is equivalent to the MVL reduction products mentioned above.

Modifications of the olefinic group in AML and its isomers include, inter alia, epoxidation, dihydroxylation, Michael addition, Diels-Alder reaction or [2+2] -cycloaddition. The reaction products are versatile in functionality and may serve as building blocks for a variety of polymers. The lactone functionality is retained in all of the above mentioned reactions. Ring-opening polymerization of these compounds can result in the formation of modified aliphatic polyesters, particularly for use as thermoplastic elastomers, unsaturated polyester resins, or polyurethanes.

The tertiary alcohols in the MVLs can be modified to form ether and ester derivatives. Functional groups that promote polymerization or properties such as solubility and adhesion may be introduced. It has been reported that methacrylates containing pendant MVL ester groups can be obtained from MVLs. It is envisaged that such difunctional adducts are capable of participating in free radical and ring opening polymerizations to produce acrylic resins and vinyl polyesters.

The MVL derived di-or polyols and acids can also serve as precursors for epoxy resins, poly (vinyl ethers), or multifunctional cyclic carbonates.

Some of the major, but not exclusive, classes of polymers that can be produced using MVL/AML or MVL/AML-derived building blocks and their applications are described below:

unsaturated polyester resin

Unsaturated polyester resins are typically prepared by a polyesterification reaction carried out in a heated stirred reactor vessel equipped with a packed column, a condenser with a steam jacket, and a water condenser. The production can be carried out in a continuous or semi-continuous (batch) esterification process. The component raw materials used as input or starting materials in the esterification process for the manufacture of unsaturated polyester resins include (abbreviations in parentheses):

(i) a saturated dibasic acid component, wherein the saturated dibasic acid component,

(ii) the component of the unsaturated dibasic acid is added,

(iii) a diol component,

(iv) a modifier component.

The saturated diacid component may comprise, inter alia: phthalic Anhydride (PA), isophthalic acid (IPA), chlorendic anhydride, adipic acid, or terephthalic acid.

The unsaturated diacid component can comprise, inter alia: maleic Anhydride (MAN) or fumaric acid.

The diol component may comprise, inter alia: propylene Glycol (PG), diethylene glycol (DEG), dipropylene glycol (DPG), Ethylene Glycol (EG) or neopentyl glycol (NPG).

The hydrocarbon modifier component may comprise, inter alia: cyclopentadiene (CP), dimethylcyclopentadiene, dicyclopentadiene (DCPD), and other plasticizers.

The UPR can be made using bio-based MVLs and related derivatives in place of or in addition to the unsaturated diacid component or diol component.

UPRs may be classified in the following ways, including: i) the content of phthalic acid or isophthalic acid component in the UPR; ii) commercial types (or uses), such as spray forming, press forming, chemical or fire resistant (each requiring a specific UPR composition); and iii) the method of application, (both with respect to reinforced or non-reinforced plastics), particularly with respect to how the UPR is used, as well as other components used to create the coating or solid object.

Phthalic acid and isophthalic acid unsaturated polyester resin

The phthalic resin can be prepared in a one-stage cooking with all the ingredients fed in one shot. Depending on the molecular weight distribution of the resulting polymer product, a typical phthalic-maleic acid resin (ratio 1:1) requires about 1-14 hours at 150 ℃ and 250 ℃.

Isophthalic acid resins can be prepared in two stages: 1) reacting the aromatic acid and the diol until a theoretically correct (calculated) amount of water has been collected and an acid number of 10-15 has been reached; 2) the material from 1) is then cooled to below 170 ℃ and fed with unsaturated acid. Depending on the molecular weight distribution of the resulting polymer product, this process may take as long as 22-32 hours at 180-230 ℃. Sometimes an esterification catalyst is used in an amount of 0.02-0.05% of the total feed.

When the polycondensation reaction described above is complete (as determined by the acid number and by the viscosity of the sample dissolved in styrene or another organic solvent), the resin is cooled to about 165 ℃ or less.

Hydroquinone (HQ) or similar compounds may be added as inhibitors and the mixture is then diluted with styrene, which is inhibited with HQ, Toluhydroquinone (THQ) or mono-tert-butylhydroquinone. T-butylcatechol and para-quinone can also be used as inhibitors.

All of the above steps are typically carried out under a blanket of nitrogen, carbon dioxide or inert gas. The slow flow of inert gas through the system helps to remove the water produced during the reaction.

The bio-based MVL based isophthalic resin can be prepared by: 1) partial and/or complete substitution of maleic anhydride with AML-derived unsaturated diacid, and/or 2) partial and/or complete substitution of diol (i.e., propylene glycol) with AML-derived diol, yields materials suitable for gel coating, chemical resistance isophthalic acid, and compression molding applications.

Commercial unsaturated polyester resin type

Spray-molded resins can generally be applied to an open mold by spraying a resin mixture (comprising unsaturated polyester + diluent, such as styrene) with a catalyst directly onto the prepared surface. The chopped glass or other material (e.g., fibers) may be first layered on the surface to be sprayed or mixed within the resin mixture and then sprayed together in combination. A typical formulation may contain 1.0-2.0 moles of phthalic anhydride, 1.0 moles of maleic anhydride, 2.1-2.8 moles of propylene glycol, and 35-45% styrene.

DCPD-based resins are fully utilized because of their lower cost and lower styrene content. In marine applications, DCPD-type resins represent over 75% of the total market. Bathroom applications of spray molded resins almost fully utilize DCPD diversity. Its main disadvantage is its relatively low resistance to oxygen and ultraviolet light. A typical formulation of a DCPD-type resin may contain 0.8 moles of DCPD, 1.0 moles of maleic anhydride, 0.4 moles of ethylene glycol, 0.2 moles of diethylene glycol, and 30-35% styrene.

Flame retardant resins are commonly used in interior construction, the use of which is governed by building codes and regulations. Flame retardancy is achieved by adding: aluminum trihydrate, chlorendic anhydride, tetrabromophthalic anhydride, dibromoneopentyl glycol, and tetrabromobisphenol a, alone or in combination with certain phosphate compounds, such as dimethyl methylphosphonate (DMMP). Flame retardant resins based on bromine compounds are the most common.

In UPR, chemical resistance is achieved by using a combination of an acid and a glycol. Isophthalic and terephthalic acids are often used in resins that require high levels of hydrolytic stability and chemical resistance. The use of neopentyl glycol imparts good water resistance to the gel coating. Trimethylpentanediol is sometimes used when a higher degree of corrosion protection is required. Cyclohexanedimethanol is sometimes used to impart outdoor durability and corrosion resistance. High performance applications requiring specific chemical and/or temperature resistance typically utilize premium grade vinyl ester resins, bisphenol a based resins, and chlorofenac based resins.

The compression molding resin typically includes maleic anhydride in a ratio of about 3.0 moles to about 1.0 mole of a precursor of an aromatic acid and a corresponding amount of propylene glycol. In some cases, no aromatic acid is used. Certain compression molding resins may be combined with thermoplastic additives to promote low profile (i.e., smooth surfaces) and reduce shrinkage (low shrinkage allows for the production of large parts with high dimensional accuracy). Such low profile/low shrinkage molding resins are typically pure (non-heteromeric) maleic anhydride-propylene glycol polyesters containing 30-40% styrene. The thermoplastic additive is typically a proprietary mixture, typically a 30-50% solution of the thermoplastic resin dissolved in styrene or a monomer mixture of predominantly styrene. The resin is typically a copolymer of styrene, vinyl acetate or other monomers. Systems including 60% UPR and 40% thermoplastic additives are often used to mold automotive parts that have relatively stringent surface requirements. Systems comprising 70% UPR and 30% thermoplastic additives are commonly used for electrical equipment housings and other similar components. The low profile/low shrinkage resin is used for press molding of resin materials such as sheet-molding compound (SMC) and bulk-molding compound (BMC). SMC is used in applications requiring electrical resistance or corrosion resistance and is often formulated at a ratio of 1.0 mole isophthalic acid to 3.0 moles maleic anhydride. Glass and other fillers are also added to provide strength. Such thickened resin systems are also used in some BMC applications.

Examples of biobased MVL based compression molding resins are unsaturated polyesters obtained from biobased AML derived diacids and diols. Similar unsaturated polyesters, partially composed of maleic anhydride or propylene glycol blocks, may also be used. As noted above, these materials are typically used with thermoplastic additives.

Unsaturated polyester resin application method

Glass Fiber Reinforced Plastic (FRP) is used for structural applications. The liquid resin is combined with the desired additives (e.g., accelerators, flame retardants, ultraviolet absorbers, and thixotropic agents) and/or fillers and pigments and then placed in contact with the glass reinforcement and catalyst. The pure resin to glass ratio is typically 65:35, while the highly filled resin to glass ratio is typically 40:40: 20. For filament winding and pultrusion applications, the ratio can be as low as 30: 70. The catalyst is added in an amount of 0.8-2 parts per 100 parts of resin and is activated by heat or curing. For room temperature curing, methyl ethyl ketone peroxide is used as a catalyst, and an accelerator such as cobalt naphthenate, cobalt octoate, Dimethylaniline (DMA), or Dimethylacetamide (DMAA) is used. Other catalysts include: tert-butyl peroxybenzoate (TBPB) for use in SMC and BMC materials; a mixture of benzoyl peroxide and Cumene Hydroperoxide (CHP) in a 2:1 molar ratio; and mixtures of CHP and benzyltrimethylammonium chloride (BTMAC) or TBPB/t-butyl peroxyoctoate (TBPO). The curing process is carried out in two stages: the first is a soft gel phase, which can be interrupted by cooling and later resumed; this is followed by a second phase which takes place with continued heating, when the exothermic reaction starts and heating has to be controlled. FRP can be used to manufacture large items such as boats and storage tanks in a manufacturing process called contact molding. Other manufacturing processes include compression molding and injection molding. Injection molding uses BMC to manufacture small parts at high throughput and high accuracy.

Non-reinforced plastics are based on liquid UPR, wherein the formulation thereof has a high diluent content in order to achieve flowability. Fillers used in such UPRs can include, inter alia, clays and calcium carbonate. Such non-reinforced UPRs are used in manufacturing processes including casting, and may also be used as: putties and filler materials (for automotive repair); potting and encapsulating compounds and surface coating resins. The topcoat resin is a monomeric polyester resin based on Methyl Methacrylate (MMA), where MMA replaces styrene, in whole or in part, and may be cured using conventional peroxide catalysts, whereas a specific UPR containing acrylate functionality may be cured by using uv light.

The physicochemical properties and use of the UPR will depend on the molar proportions of the raw materials used in the polyesterification process. The average raw material requirements for different types of unsaturated polyester resins for various applications may include (molar ratios):

general spray forming

Conventional ortho-type: 1.5 PA; 1.2 MAN; 2.2 PG; 0.5 DEG.

DCPD type: 0.8 DCPD; 1.0 MAN; 0.4 EG; 0.2 DEG.

And (3) pressure forming: 0.2 PA; 1.2 IPA; 3.7 MAN; 2.5 PG; 1.5 DEG; 0.2 DPG; 0.5 NPG.

Chemical resistance

Isophthalic acid: 1.0 IPA; 1.0 MAN; 2.0 PG.

Gel coating: 1.5 IPA; 1.0 MAN; 1.5 PG; 2.5 NPG.

non-FRP: 3.5 PA; 2.0 MAN; 2.0 PG; 3.0 DEG; 0.5 DPG.

Exemplary polymers

In the chemical structures depicted herein, wavy lines perpendicular to the chemical bonds are used

To indicate that the structure shown is a smaller part (portion) of a larger chemical entity and, therefore, the wavy line perpendicular to the chemical bond indicates a chemical connection point between two chemical entities, e.g., a chemical connection point of the depicted structure to the rest of the polymer backbone or other chemical segments in the polymer chain.

However, the bonds drawn as wavy lines themselves represent chemical bonds indicating the presence of stereochemically isomeric forms, in pure or mixed form. For example, formula (II)

Represents (R) -2-bromo-2-chlorobutane, (S) -2-bromo-2-chlorobutane or a mixture thereof. In another example, formula (II) is

Represents (Z) -2-butene, (E) -2-butene or a mixture thereof.

In one aspect, the present invention relates to a polyester polymer synthesized using bio-based MVLs and comprising repeating monomer units comprising distinct moieties. In one or more embodiments, the polyester comprises one or more moieties represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), and/or formula (Ig). In one or more embodiments, the polyester polymer comprises a plurality of moieties represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), and/or formula (Ig):

wherein, independently at each occurrence:

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

y is-O-, -S-, -N (H) or-N (R)₃)；

R₃Is C₁-C₆Alkyl, cycloalkyl or aryl; and is

In a second aspect, the present invention relates to a polyester comprising one or more moieties represented by formula (IIa), formula (IIb) and/or formula (IIc):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group; and is

R₂Is C₁-C₆An alkyl group.

In certain embodiments, the present invention relates to any one of the aforementioned polyester polymers further comprising monomeric, oligomeric, or polymeric repeat units (blocks) represented by formula (III)

Wherein, independently at each occurrence,

x is halogen or C₁-C₆An alkyl group;

t1 is 0,1, 2,3 or 4;

Y₁、Y₂、Y₃、Y₄、Y₅and Y₆Independently is H or C₁-C₆An alkyl group;

o is 0,1, 2,3 or 4;

p is an integer from 1 to 50; and is

q is an integer of 2 to 100,000.

In another embodiment, the present invention relates to the aforementioned polyester block copolymer, further comprising monomeric, oligomeric, or polymeric repeat units (blocks) represented by formula (IV):

wherein, independently at each occurrence,

z is halogen or C₁-C₆An alkyl group;

t2 is 0,1, 2,3 or 4;

Y'₁、Y'₂、Y'₃、Y'₄、Y'₅and Y'₆Independently is H or C₁-C₆An alkyl group;

r is 0,1, 2,3 or 4;

s is an integer from 1 to 50; and is

t is an integer of 2 to 100,000.

Wherein, independently at each occurrence,

r 'and R' are independently H or C₁-C₆An alkyl group;

Y”₁、Y”₂、Y”₃、Y”₄、Y”₅and Y "₆Independently is H or C₁-C₆An alkyl group;

u is 0,1, 2,3 or 4;

w is an integer from 1 to 50; and is

v is an integer from 2 to 100,000.

In another embodiment, the present invention relates to any one of the aforementioned polyester block copolymers, further comprising a moiety represented by formula (VI):

wherein, independently at each occurrence,

Y”'₁、Y”'₂、Y”'₃、Y”'₄、Y”'₅and Y'₆Independently is H or C₁-C₆An alkyl group.

In another embodiment, the present invention relates to any one of the aforementioned polyester block copolymers, further comprising a moiety represented by formula (XXVII):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group; and is

n is an integer of 1 to 100,000.

In certain embodiments, the present invention relates to monomeric, oligomeric, or polymeric repeat units represented by formula (VIII):

wherein, independently at each occurrence,

R₁and R₄Independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group; and is

n is an integer of 2 to 100,000.

In certain embodiments, the present invention relates to the aforementioned oligomeric or polymeric repeat unit represented by formula (VIII) further comprising another monomeric, oligomeric or polymeric repeat unit (block) represented by formula (IX):

wherein, independently at each occurrence,

R₁and R₄Independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

n is an integer of 1 to 10,000;

R₅is hydrogen, straight or branched chain alkyl, cycloalkyl, aryl or heteroaryl;

R₃is straight or branched C₁-C₆Alkyl, cycloalkyl, aryl or heteroaryl; and is

Y is-O-, -S-, -N (H) or-N (R)₃)。

In certain embodiments, the present invention relates to the aforementioned polymer blocks, further comprising another monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (X):

wherein, independently at each occurrence,

R₁、R₄independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

R₃is C₁-C₆Alkyl, cycloalkyl or aryl;

y is-O-, -S-, -N (H) or-N (R)₃) (ii) a And is

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of poly (isoprene acetate).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of poly (ethylene) or poly (propylene).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of poly (vinyl alcohol) or poly (vinyl ester).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers further comprising a block of poly (acrylic acid) or poly (methyl acrylate).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of poly (methacrylic acid) or poly (methyl methacrylate).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of poly (acrylamide) or poly (methacrylamide).

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, further comprising a block of polystyrene.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein R is₁Is H; and R is₂is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein R is₄is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is-n (h), and Q is ethyl, n-propyl, n-butyl, n-pentyl, or n-hexyl.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is-O-.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein T is₁Is 0.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, whereinT₂Is 0.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is₁、Y₂、Y₃、Y₄、 Y₅And Y₆Is H.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is₁、Y₂、Y₅And Y₆Is H; and Y is₃And Y₄is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is₁、Y₂、Y₄、Y₅And Y₆Is H; and Y is₃is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y is₁Or Y₅is-CH₃。

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein Y'₁、Y'₂、Y'₃、Y'₄、 Y'₅And Y'₆Is H.

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein Y'₁、Y'₂、Y'₅And Y'₆Is H; and Y'₃And Y'₄is-CH₃。

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein Y'₁、Y'₂、Y'₄、Y'₅And Y'₆Is H; and Y'₃is-CH₃。

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein Y'₁Or Y'₅is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y "₁、Y”₂、Y”₃、 Y”₄、Y”₅And Y "₆Is H.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y "₁、Y”₂、Y”₅And Y "₆Is H; and Y "₃And Y "₄is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y "₁、Y”₂、Y”₄、 Y”₅And Y "₆Is H; and Y "₃is-CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein Y "₁Or Y "₅is-CH₃。

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein Y ″'₁、Y”'₂、Y”'₃、 Y”'₄、Y”'₅And Y'₆Is H.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein p is 1 or 2.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein s is 1 or 2.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein o is 0 or 1.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein o is 0.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein r is 0 or 1.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein r is 0.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein u is 0 or 1.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein u is 0.

Polyurethane

Polyurethanes are generally prepared from the following raw materials:

(i) a polyol component,

(ii) a diisocyanate and/or polyisocyanate component,

(iii) a crosslinker (or chain extender) component, and

(iv) a blowing agent component.

The polyol component may comprise polyethers, such as, inter alia: poly (propylene glycol), poly (ethylene glycol), poly (propylene glycol-co-ethylene glycol), or poly (butylene glycol). The polyol component may also comprise polyesters derived from inter alia adipic acid, phthalic acid, diethylene glycol and 1, 2-propanediol. Its hydroxyl functionality is typically about 2 and its average molecular weight is between 200 and 10,000 g/mole.

The diisocyanate and/or polyisocyanate component may comprise, inter alia: toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), triphenylmethane triisocyanate.

The crosslinking agent (or chain extender) may comprise, inter alia: glycerol, trimethylolpropane, ethylene glycol, ethylenediamine and phenylenediamine.

The blowing agent component may comprise, inter alia: pentane, carbon dioxide, dichloromethane and water.

In making the polyurethane, the polyol and/or chain extender may be replaced or supplemented with bio-based MVLs and related derivatives.

Polyurethanes can be characterized by their thermoplastic or thermoset chemical structure and their hard solid, soft elastomeric or foam physical appearance. They are used in commercial applications classified as flexible flat panels (in particular furniture, bedding, automobiles); flexible molded foams (especially car seats, bedding); rigid foams (especially electrical equipment, insulation, automobiles); solid elastomers (especially coatings, elastomers, adhesives, medical); reaction Injection Molding (RIM) (especially mechanical, automotive); carpet backing (especially integral attached cushion); and two-component formulations (especially casting, potting, sealants).

The polyurethanes may also be characterized by a process for their preparation: i) no solvent, ii) in solution, or iii) aqueous dispersion.

Polyurethane dispersion

Polyurethane dispersions are aqueous dispersions of high molecular weight polyurethanes or poly (urethane-ureas) that are stabilized by ionic (i.e., anionic or cationic) or hydrophilic nonionic groups in the polyurethane backbone. Characteristics of the end-use application include tack, solvent and abrasion resistance, flexibility, and toughness.

The aqueous anionic polyurethane dispersion may be prepared by a solvent process. To a stirred vessel are added a diisocyanate or polyisocyanate, a diol or polyol and an acid diol, and a solvent, typically in a 4:2:1 molar ratio. The acid diol typically contains a carboxylic acid or sulfonic acid group, such as dimethylolpropionic acid or dimethylolbutyric acid. As solvents, in particular, propiophenone or N-methylpyrrolidone can be employed. To this mixture is typically added 0.1 mole% of a catalyst, such as dibutyltin dilaurate (DBTDL). Other catalysts, such as triethylenediamine (DABCO), dimethylethanolamine, stannous octoate, or bismuth carboxylate, may also be used. The polyurethane prepolymer is then formed at elevated temperatures of 50-100 ℃ until the desired isocyanate content, typically 0.1 to 10%, is reached. After cooling the mixture to below 90 ℃, the solution is neutralized by adding a base (such as triethylamine) and water is added to form a dispersion. The polyurethane chain may then be extended by further adding a diamine chain extender (e.g., ethylene diamine).

In one variation, the prepolymer solution may be formed by reacting a diisocyanate or polyisocyanate with a diol or polyol in acetone at a molar ratio of between 1.2 and 2.5. At temperatures below 50 ℃, chain extenders, typically sulfonate-functional diamines such as 1, 1-diaminomethanesulfonic acid, 2- [ (2-aminoethyl) amino ] ethanesulfonic acid, or 1, 1-diaminopropanesulfonic acid, are added to introduce water soluble/dispersible groups. The addition of water and base produces an anionic aqueous polymer dispersion.

Removal of the acetone or N-methylpyrrolidone solvent may be necessary and effected by distillation to produce a polyurethane dispersion having a solids content of 30 to 50%. For textile coating and impregnation applications, a solids content of up to 60% is preferred.

The use of polyurethane dispersions is for the coating of wood floors, plastics, or as a base coat for automobiles, for finishes for wood, glass fibers or leather, and also as adhesives.

With respect to leather finishes, after extension, the polyurethane dispersions prepared as described above may be thickened by the addition of a polymeric thickener selected between polyurethane or acrylic polymers or derivatives of modified polysaccharides. It typically constitutes between 0.1% and 7% by weight of the dispersion. In addition, pigments, flame retardants, and sensory additives may also be used. Impregnation of the fabric may be carried out by any suitable method known in the art. Examples include dipping, spraying or knife scraping. After impregnation, the impregnated textile may be freed of excess resin to leave a desired amount of dispersion within the textile. This is typically accomplished by passing the impregnated textile through a rubber roller.

Polyurethane foam

Polyurethane foams are typically produced in a solvent-free process. Common uses for flexible foams are especially upholstered furniture, mattresses, car seats.

Typically an 80:20 isomeric mixture of 2, 4-and 2, 6-Toluene Diisocyanate (TDI) is used to form flexible and semi-flexible foams, however modified TDI, MDI or polyphenyl diisocyanates are generally selected for rigid foams. With flexible foams, diisocyanates are reacted with polyether polyols, usually based on polyethylene oxide or polypropylene oxide, in the presence of blowing agents and/or auxiliary blowing agents, and the number of reactive hydroxyl groups is between 2 and 3. A low boiling point gas such as trichloro-fluoro-acid salt and/or water may be added to cause foaming. Other auxiliary blowing agents are, in particular, methylene chloride, n-pentane, cyclopentane and acetone.

Polyurethane foams are generally prepared by a one-shot process. A typical formulation for a one-shot flexible foam is 100 parts polyether polyol (usually a mixture of diols and triols), 40 parts toluene diisocyanate, 4 parts water, 1 part surfactant, 1 part amine catalyst, and 0.5 part tin catalyst. Common surfactants are silicone-based polymers and copolymers. Stannous oleate, stannous octoate and dibutyltin dilaurate may be used as tin catalysts, and DABCO, triethylamine, N-ethylmorpholine and N, N' -tetramethyl-1, 3-butanediamine may be used as amine catalysts.

In continuous plate manufacturing, the chemical components mentioned above are delivered at a fixed rate to a mixing head which moves on a conveyor belt into a continuous mold typically formed by a conveyor belt and adjustable side plates, outputting at 100-. Temperature curing may be performed in a curing oven until no traces are present (15min to 24 h). Typically, flat sheet stock materials are further processed, particularly by cross-cut saws, horizontal and vertical trimmers, slicers, and wire cutters. Centrifugal peeling and horizontal table splitting can be used to obtain flexible flat products for mattresses, cushions, pillows, sponges, cushioning materials, and other materials.

The biobased MVL based polyurethanes can be illustrated by the following: partially or fully replacing the polyol with a MVL-derived polyester polyol, and partially or fully replacing the chain extender with a MVL-derived diol and/or triol.

Exemplary polymers

In another aspect, the present invention relates to a polyurethane polymer synthesized using bio-based MVLs and comprising repeating monomeric units comprising distinct moieties. In one or more embodiments, the polyurethane comprises one or more moieties represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), and/or formula (Ig), as defined above. In one or more embodiments, the polyurethane polymer comprises a plurality of moieties represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), formula (If), and/or formula (Ig), as defined above.

In certain embodiments, the present invention relates to the aforementioned polyurethane polymer, further comprising a second monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XI):

wherein, independently at each occurrence,

R'₁、R'₂、R'₃、R'₄、R'₅and R'₆Independently is H or C₁-C₆An alkyl group;

l' is 0,1, 2,3 or 4;

n' is an integer from 2 to 1,000;

m' is an integer of 1 to 100,000; and is

Q' is a monoatomic or polyatomic linkage independently selected from: hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, aryl, substituted aryl, heteroatom-containing aryl, and substituted heteroatom-containing aryl.

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein R'₁、R'₂、R'₃、R'₄、 R'₅And R'₆Is H, and l' is 2.

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein R'₁Or R'₅Is CH₃And l' is 0.

In certain embodiments, the present disclosure relates to any one of the foregoing block copolymers, wherein R'₁、R'₂、R'₃、R'₄、 R'₅And R'₆Is H, and l' is 0.

In certain embodiments, the present invention relates to any one of the aforementioned polyurethane blocks, further comprising a third monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XII):

wherein, independently at each occurrence,

R”₁、R”₂、R”₃、R”₄、R”₅、R”₆、R”₇and R "₈Independently is H or C₁-C₆An alkyl group;

n "is an integer from 2 to 100,000;

m "is an integer from 0 to 4;

l "is an integer from 0 to 4;

k "is an integer from 2 to 1,000; and is

Q "is a monoatomic or polyatomic linkage independently selected from: hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, aryl, substituted aryl, heteroatom-containing aryl, and substituted heteroatom-containing aryl.

In certain embodiments, the present invention relates to any one of the aforementioned block copolymers, wherein R "₁、R”₂、R”₃、 R”₄、R”₅、R”₆、R”₇And R "₈Is H, l "is 0 or 2, and m" is 4.

wherein, independently at each occurrence,

R”'₁、R”'₂、R”'₃、R”'₄、R”'₅、R”'₆、R”'₇and R'₈Independently is H or C₁-C₆An alkyl group;

n' "is an integer from 2 to 100,000;

m' "is an integer of 0 to 100;

l' "is an integer from 1 to 6;

o' "is an integer from 0 to 6;

p' "is an integer from 1 to 100; and is

Q' "is a monoatomic or polyatomic linkage independently selected from: hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, aryl, substituted aryl, heteroatom-containing aryl, and substituted heteroatom-containing aryl.

In certain embodiments, the present disclosure relates to any one of the foregoing polyurethane block copolymers, wherein R ″'₁、 R”'₂、R”'₃、R”'₄、R”'₅、R”'₆、R”'₇And R'₈Is H, l "is 5, o '" is 0, and p' "is 1 or 2.

In certain embodiments, the present disclosure relates to any one of the foregoing polyurethane block copolymers, wherein R ″'₅And R'₆Is CH₃L "is 5, o '" is 1, and p' "is 1.

In certain embodiments, the present invention relates to any one of the aforementioned polyurethane copolymers, wherein Q ', Q ", and/or Q'" comprises a structure represented by formula (XIIIa), formula (XIIIb), formula (XIIIc), formula (XIIId), formula (XIIIe), formula (XIIIf), formula (XIIIg), formula (XIIIh), and/or formula (XIIIi):

in certain embodiments, the present invention relates to any one of the aforementioned polyurethane blocks, further comprising another monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XIVa), formula (XIVb), and/or formula (XIVc):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

y is-O-, -S-, -N (H) or-N (R)₃)；

R₃Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group; and is

R₆Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group. It is preferably represented by formula (XIIIa), formula (XIIIb), formula (XIIic), formula (XIIId), formula (XIIIE), formula (XIIif) and/or formula (XIIIg).

In certain embodiments, the present invention relates to any one of the aforementioned polyurethane block copolymers, wherein R is₁Is H, and R₂Is CH₃。

In certain embodiments, the present invention relates to any one of the aforementioned polyurethane block copolymers, wherein R is₁Is H, R₂Is CH₃And Y is-N (H).

Glycidyl ethers

Epoxy resins are an important class of thermosets. They are generally formulated from diepoxy and/or polyepoxy resins, which may be diluted with reactive and/or non-reactive fillers and cured with hardeners. Curing can also be achieved by light or temperature.

The resin component is a low to high molecular weight molecule containing at least two epoxy groups. It may include, inter alia, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and phenol novolac polyglycidyl ethers. Reactive diluents or reactive fillers are aliphatic monoglycidyl and diglycidyl ethers, such as, in particular, dodecanol glycidyl ether, 2-ethylhexyl glycidyl ether or neopentyl glycol diglycidyl ether.

The hardener component may be selected from one of the following classes: i) a polyfunctional nucleophile (such as, inter alia, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, menthanediamine or a polysulfide), ii) a cyclic anhydride (such as, inter alia, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, maleic anhydride), or iii) a Lewis acid or base catalyst.

Curing with nucleophilic hardeners can occur at ambient conditions, while anhydride and lewis acids or base catalyzed curing occurs at elevated temperatures of 80-150 ℃.

Exemplary glycidyl ethers

In another aspect, the present invention relates to a chemical molecule (non-polymeric compound) synthesized using bio-based MVL, represented by formula (XVa), formula (XVb), formula (XVc), formula (XVd), formula (XVe), formula (XVf), formula (XVg), formula (XVh), formula (XVi), formula (XVj), formula (XVk), formula (XVl), formula (XVm), formula (XVn) and/or formula (XVo):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

q is a monoatomic or polyatomic linkage independently selected from: hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, aryl, substituted aryl, heteroatom-containing aryl, and substituted heteroatom-containing aryl;

y is-O-, -S-, -N (H) or-N (R)₃) (ii) a And is

R₃Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group.

In another aspect, the invention relates to a chemical molecule (non-polymeric compound) synthesized using bio-based AML and represented by formula (XXVI):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group; and is

R₂Is C₁-C₆An alkyl group.

The invention also relates to polymers derived from the above non-polymeric glycidyl ethers and epoxy compounds.

Illustrative omega-alkenyl ethers and esters

In another aspect, the invention relates to a chemical molecule (non-polymeric compound) synthesized using bio-based MVL and represented by formula (XVIa), formula (XVIb), formula (XVIc), formula (XVId), formula (XVIe), formula (XVIf), formula (XVIg), formula (XVIh), formula (XVIi), formula (XVIj), formula (XVIk), formula (XVIl), formula (XVIm), formula (XVIn), and/or formula (XVIo):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

n is an integer from 0 to 50;

y is-O-, -S-, -N (H) or-N (R)₃) (ii) a And is

R₃Is a linear or branched alkyl, cycloalkyl, aryl or heteroaryl group.

The present invention also relates to polymers derived from the above non-polymeric omega-alkenyl ether and ester compounds.

Exemplary Cyclic carbonates

In another aspect, the invention relates to a chemical molecule (non-polymeric compound) synthesized using bio-based MVL, represented by formula (XVIIa), formula (XVIIb), formula (XVIIc), formula (XVIId), formula (xviiie), formula (xviiif), and/or formula (xviiig):

wherein, independently at each occurrence,

R₁independently selected from H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

y is-O-, -S-, -N (H) or-N (R)₃)；

R₃Is alkyl, cycloalkyl or aryl; and is

Exemplary polycarbonates

In another aspect, the invention relates to a polymer comprising recurring monomers represented by formula (XVIIIa), formula (XVIIb), formula (XVIIIc), formula (XVIIId), formula (XVIIIe), formula (XVIIIf), and/or formula (XVIIIg):

wherein, independently at each occurrence,

R₁independently is H or C₁-C₆An alkyl group;

R₂is C₁-C₆An alkyl group;

y is-O-, -S-, -N (H) or-N (R)₃)；

R₃Is C₁-C₆Alkyl, cycloalkyl or aryl;

n is an integer from 2 to 100,000; and is

In another embodiment, the present invention relates to the aforementioned polycarbonate, further comprising a second monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XIX):

wherein n is an integer from 1 to 100,000.

Exemplary polyamides

In one aspect, the present invention relates to a polyamide polymer synthesized using bio-based MVLs and comprising repeating monomer units comprising distinct moieties. In one or more embodiments, the polyamide comprises one or more moieties represented by formula (XXa), formula (XXb), and/or formula (XXc):

wherein, independently at each occurrence,

R₁independently is H or C₁-C₆An alkyl group; and is

R₂Is C₁-C₆An alkyl group.

In another embodiment, the present invention relates to the aforementioned polyamide polymer, further comprising a second monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XXI):

wherein n is an integer from 1 to 100,100.

In another embodiment, the present invention relates to the aforementioned polyamide polymer, further comprising a third monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XXII):

wherein n is an integer from 1 to 100,100;

m is an integer from 1 to 50; and is

p is an integer from 1 to 50.

In another embodiment, the present invention relates to the aforementioned polyamide polymer, further comprising a fourth monomeric, oligomeric, or polymeric repeat unit (block) represented by formula (XXIII):

wherein n is an integer from 1 to 100,100; and is

m is an integer of 0 to 50.

Biobased compositions are also described herein. The compositions comprise one or more of the above bio-based MVL precursor compounds, derivatives thereof, and/or polymers dispersed or dissolved in a suitable solvent system. Such compositions will have a variety of uses, depending on the particular precursor compound or polymer used, as discussed in part above and advantageously based on renewable materials, rather than being derived primarily from petroleum (non-renewable) sources.

Other advantages of various embodiments of the present invention will be apparent to those of ordinary skill in the art upon review of the disclosure herein and the following examples. It should be understood that the various embodiments described herein are not necessarily mutually exclusive, unless otherwise indicated herein. For example, features described or depicted in one embodiment may also be included in other embodiments, but are not necessarily included. Thus, the present disclosure encompasses various combinations and/or integrations of the specific embodiments described herein.

As used herein, the phrase "and/or," when used in a listing of two or more items, means that any one of the listed items can be employed alone or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing or excluding component A, B and/or C, the composition may contain or exclude: a alone; b alone; c alone; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B and C.

The present description also uses numerical ranges to quantify certain parameters relating to various embodiments of the invention. It should be understood that when numerical ranges are provided, such ranges are considered to provide literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of about 10 to about 100 provides literal support for a claim reciting "greater than about 10" (without an upper bound) and a claim reciting "less than about 100" (without a lower bound).

Examples of the invention

The following examples illustrate the methods and compounds according to the present invention. It is to be understood, however, that these examples are provided by way of illustration and nothing therein should be taken as a limitation on the scope of the invention.

Synthesis of Bio-based MVL derived Compounds

EXAMPLE 1 Synthesis of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide (MVLea)

Such compounds are represented by formulas (Id), (XIVa), (Xvf), (XVIE), (XVIe), (XVIIe) and (XXIVb). The bio-based (R) - (-) -mevalonolactone (3.30g, 25.4mmol) was dissolved in the volume equivalent of THF and 1.30g (21.3mmol) ethanolamine was added dropwise to give a pale yellow solution. The reaction was stirred for 12h and then precipitated into 40mL of diethyl ether. The supernatant was decanted off and the residue was washed four times with 20mL of ether and then dried in vacuo overnight to constant weight, yielding 4.02g of a light yellow oil (98%).¹NMR(500MHz,DMSO) δ7.95(t,J＝5.2Hz,1H),4.94(s,1H),4.69(s,1H),4.39(s,1H),3.52(dd,J＝11.6,7.1Hz, 2H),3.39(t,J＝6.0Hz,2H),3.13(q,J＝6.0Hz,2H),2.22(s,2H),1.61(td,J＝7.1,2.9Hz, 2H),1.10(s,3H)。¹H NMR(500MHz,MeOD)δ4.67(s,3H),3.52(dd,J＝13.9,7.1Hz, 2H),3.38(t,J＝5.7Hz,2H),3.16-2.96(m,2H),2.18(q,J＝14.1Hz,2H),1.57(td,J＝6.9, 5.4Hz,2H),1.04(s,3H)。¹³C NMR(126MHz,MeOD)δ174.4,72.1,61.5,59.2,48.0,44.4, 42.8,27.5。

EXAMPLE 2 Synthesis of 3, 5-dihydroxy-N- (5-hydroxypentyl) -3-methylpentanamide (MVLpa)

Such compounds are represented by formulas (Id), (XIVa), (Xvf), (XVIE), (XVIe), (XVIIe) and (XXIVb). Bio-based (R) - (-) -mevalonolactone (1.1g, 8.5mmol) was dissolved in the volume equivalent of THF and 0.79g (5.9mmol) of 5-amino-1-pentanol was added dropwise, yielding a pale yellow solution. The reaction was stirred for 12h and then precipitated into 40mL of diethyl ether. The supernatant was decanted off and the residue was washed four times with 20mL of ether and then dried in vacuo overnight to constant weight, yielding 1.28g of a light yellow oil (93% yield).¹HNMR(500MHz, DMSO)δ7.92(t,J＝5.5Hz,1H),4.97(s,1H),4.40(s,2H),3.64-3.46(m,2H),3.37(t, J＝6.7Hz,2H),3.04(dd,J＝12.7,6.9Hz,2H),2.20(s,2H),1.60(td,J＝6.9,2.0Hz,2H), 1.47-1.33(m,4H),1.32-1.23(m,2H),1.10(s,3H)。

EXAMPLE 3 Synthesis of N, N' - (Hexane-1, 6-diyl) bis (3, 5-dihydroxy-3-methylpentanamide) (hmMVL)₂)

Such compounds are represented by the formulae (Ig), (XVi), (XVj) and (XVIE), (XVIg), (XVIIg), (XVIF), (XVIg), (XIVa) and (XXIVe). Bio-based (R) - (-) -mevalonolactone (1.1g, 8.5mmol) was dissolved in the volume equivalent of THF and 0.45g (3.9mmol) of 1, 6-hexanediamine was added dropwise, yielding a pale yellow solution. The reaction was stirred for 12h and then precipitated into 40mL of diethyl ether. The supernatant was decanted off and the residue was washed four times with 20mL of ether and then dried in vacuo overnight to constant weight, yielding 1.41g of a highly viscous pale yellow oil (96% yield).¹H NMR(500MHz,DMSO)δ7.92(t,J＝5.5Hz,2H),4.96(s,2H),4.40 (s,2H),3.60-3.47(m,4H),3.34(s,2H),3.03(dd,J＝12.7,6.8Hz,4H),2.20(s,4H),1.60 (td,J＝6.8,1.9Hz,4H),1.41-1.34(m,4H),1.28-1.22(m,4H),1.10(s,6H)。

EXAMPLE 4 Synthesis of 3-methylpent-2-ene-1, 5-diol (AML diol)

Such compounds are represented by the formulae (Ib), (XVc), (XVIb), (XVIIb) and (XXvb). Based on the general stereoselective synthesis of olefins (A general stereoselective synthesis of olefins); J.W. Commforth, R.H.Commforth, K.K.Mathew journal of the chemical society (J.chem.Soc.), 1959,112-127 synthesis and are briefly described herein.

To the flame dried flask was added 100mL of anhydrous ether, followed by 2.7g of lithium aluminum hydride under a nitrogen blanket. 8g of bio-based AML was added dropwise and the mixture was stirred at room temperature for 16h and then under reflux for 4 h. The reaction was quenched by the sequential addition of 10mL of diethyl ether containing 10mL of ethyl acetate, 20mL of saturated ammonium chloride solution. The filtered residue was extracted with 100mL of hot methanol, then the methanol was evaporated off, and that residue was extracted with 3 × 30mL of diethyl ether. The combined ether phases were evaporated and the residue was distilled twice to yield 2.8g of the title compound as a colorless oil.¹H NMR(500MHz,DMSO)δ5.39-5.23(m,1H),4.50(s,2H),3.91(dd,J＝ 6.7,0.8Hz,2H),3.41(t,J＝7.1Hz,2H),2.16(t,J＝7.1Hz,2H),1.68(dd,J＝2.4,1.1Hz, 3H)。

Other stereoisomers of (Z) -3-methylpent-2-ene-1, 5-diol, i.e. (E) -3-methylpent-2-ene-1, 5-diol or 3-methylenepent-1, 5-diol, or mixtures of two or three of said compounds, may be obtained by dehydration of the 3-methylpent-1, 3, 5-triol mentioned in example 5. Different reaction conditions such as temperature, solvent, concentration, and nature of the catalytic acid and/or base affect the dehydration mechanism and can be used to alter the product mixture composition.

EXAMPLE 5 Synthesis of 3-methylpentane-1, 3, 5-triol (MVL triol)

Such compounds are represented by the formulae (Ia), (XIVb), (XVa), (XVb), (XXVa), (XVIa), (XVIIa) and (XVIIa). Synthesized according to the prior art: chemical Synthesis of mevalonate 5-Phosphate, Isopentenyl Pyrophosphate and Related Compounds (The Chemical Synthesis of mevalonate Acid 5-Phosphate, Isoprenyl Phosphate, and Related Compounds), C.D.Foote, F.Wold Biochemistry 1963,2(6), 1254-1258. Such compounds incorporated into the polymer are represented by formula (Ia). It can be used in unsaturated polyester resins (examples 9 to 16), polyesterols for polyurethanes or conventional polyesters. It can also be used as a precursor for diglycidyl ethers, i.e. of formula (XVa).

To a dry two-necked flask containing 30mL of lithium aluminum hydride (1M in THF, 1.3 equivalents) in 50mL of anhydrous THF was slowly added a solution of 3g of bio-based MVL (23.1mmol) in 5mL of anhydrous THF, causing the formation of a white precipitate. The solution was heated to reflux for 18 h. The reaction was quenched by slowly adding 100mL of water at 0 ℃ and the inorganic salts were filtered off. The filter cake was washed with 100mL of ethanol and the combined organic phases were evaporated to dryness. Kugeldanif distillation (Kugelrohr distillation) of the yellow syrup gave 2.1g of a colorless oil.¹H NMR(500 MHz,DMSO)δ4.33(t,J＝5.0Hz,2H),4.28(s,1H),3.51(dt,J＝7.3,5.0Hz,4H),1.55(dd, J＝7.6,6.6Hz,4H),1.06(s,3H)。

Example 6 Synthesis of 3-methylpentane-1, 5-diol (MVL diol) (prophetic)

Such compounds are represented by formulas (Ic), (XVd), (XVId), (XVIic), (XVIIc) and (XXVc). In a typical experiment, 2.00g of biobased AML, 1 mol% [ Rh (acac) (CO) ] was added to Schlenk tube₂]And 1Mol% [ Mo (CO)₆]Dissolved in 40g of 1, 4-dioxane and transferred to a 300mL stainless steel autoclave evacuated to vacuum. The vessel was pressurized with 120 bar hydrogen and heated to 200 ℃ over 20min, generating a hydrogen pressure of 150 bar at the reaction temperature. After the stirrer had been accelerated to 700rpm, a reaction time of 2h was taken. After cooling the reaction mixture to room temperature, the solvent was evaporated. The product was purified by vacuum distillation. (adapted from Bimetallic-Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols (molar-Catalyzed Reduction of Carboxylic Acids and Lactones to Alcohols and Diols.) A. Behr, V.A. Brehme, advanced Synthesis and catalysis (Adv. Synth. Cat.) 2002,344,525-

EXAMPLE 7 Synthesis of 3-methylpent-2-enedioic acid (AML diacid) (prophetic)

Such compounds are represented by the formulae (IIa), (XVl), (XVIL), (XXa) and (XXvb). Bio-based AML (5g) was added slowly to 20mL nitric acid (70%) and stirred at 50 ℃ for 4 h. All volatiles were distilled off and the residue was recrystallized from n-butyl acetate.

Analogously to (Z) -3-methylpent-2-ene-1, 5-diol (example 4), the other stereoisomer, i.e. (E) -3-methylpent-2-ene-dioic acid or 3-methyleneglutaric acid, or a mixture of two or three of the compounds mentioned can be obtained by dehydration of 3-hydroxy-3-methylpent-3-anedioic acid. Different reaction conditions such as temperature, solvent, concentration, and nature of the catalytic acid and/or base affect the dehydration mechanism and can be used to alter the product mixture composition.

EXAMPLE 8 Synthesis of 3-hydroxy-3-methylglutaric acid (MVL diacid)

Such compounds are represented by the formulae (IIb), (XIVc), (Xvm), (XVn), (XVim), (XVn), (XXb) and (XXve). Synthesized by adapting the prior art: "Synthesis of Mevalonolactone from 4- (Hydroxyethyl) -4-methyl-1, 3-dioxane" (Synthesis of Mevalonolactone from 4- (hydroxyyethyl) -4-methyl-1, 3-dioxane) "M.S. Sargsian, A.T. Manukyan, S.A.Mkrytoyan, A.A.Gevorkyan" Natural Compounds chemistry (chem. nat. Comp.) 1990,26(1), 24-25.

Under stirring, a few drops of bio-based MVL were added to 20mL of 69-70% nitric acid. Once the reaction start was observed by significant darkening of the solution, the remaining bio-based MVL (4.1 g total) was added slowly and the solution was cooled in an ice bath. After the addition was complete, the solution was stirred at 40 ℃ for 4 h. All volatiles were distilled off under reduced pressure at a temperature below 50 ℃. The yellow oil was recrystallized from hot n-butyl acetate to give 2.9g of the title compound as an off-white powder (57% yield).¹H NMR(500MHz,DMSO)δ9.87(s,3H),2.44(d,J＝13.4Hz,2H),2.37(d,J＝13.4 Hz,2H),1.20(s,3H)。

Synthesis of unsaturated polyester resin

Example 9 Synthesis of ortho UPR resin containing moieties of formula (Ib)

Such polymers are represented by the formulae (Ib), (III) and (V). A reaction vessel equipped with a thermocouple, distillation bridge and nitrogen inlet was charged with 2.81g of phthalic anhydride (19mmol), 2.78g of maleic anhydride (28mmol), 0.90g of 1, 2-propanediol (12mmol), 2.71g of 2-methylpropane-1, 3-diol (30mmol) and 0.93g of 3-methylpent-2-ene-1, 5-diol (8 mmol). The reaction was heated to 100 ℃ under a slow nitrogen sparge, the temperature was raised to 190 ℃ over 2 hours, and the reaction was allowed to continue at that temperature for 8 hours. The reaction was cooled to 130 ℃,2 mg of 4-tert-butyl-catechol was added, and cooled to room temperature. The final resin had an acid value of 23mg KOH/g, and M_n＝2.9kg mol^-1，M_w/M_n10.92 (compare narrow PS standard in THF eluent).

EXAMPLE 10 crosslinking of ortho-UPR resins containing moieties of formula (Ib)

Such thermosets are represented by the formulae (Ib), (III) and (V). To the unsaturated polyester resin obtained in example 9, styrene was added in a weight ratio of 40:60, and 4, N-trimethylaniline (0.08 wt%) and benzoyl peroxide (1.0 wt%) were additionally added. The formulation was mechanically stirred to achieve complete mixing, poured into an aluminum pan, and cured at 50 ℃ for 24 hours to obtain duroplastic properties.

EXAMPLE 11 Synthesis of ortho-UPR resins containing moieties of the formulae (IIa) and (IIb)

Such polymers are represented by the formulae (IIa), (IIb), (III) and (V). A reaction vessel equipped with a thermocouple, a distillation bridge and a nitrogen inlet was charged with 0.90g of 1, 2-propanediol, 3.44g of 2-methylpropane-1, 3-diol, 1.41g of phthalic anhydride and 2.81g of maleic anhydride and heated to 130 ℃ under a stream of dry nitrogen for 1 hour. 1.55 g of 3-hydroxy-3-methylglutaric acid and 1mg of monobutyltin oxide are added and the temperature is raised to 190 ℃ within 6 hours and stirred at 190 ℃ for a further 2 hours. After the desired acid number was reached, the mixture was cooled to 100 ℃, 1mg of 4-tert-butyl-catechol was added, and the resin was discharged. The final resin had an acid number of 31mg KOH/g, M_n＝1.9kg mol^-1And M is_w/M_n3.07 (compare narrow PS standard in THF eluent). In the final resin, less than 10 mole% of the 3-hydroxy-3-methylglutarate is partially dehydrated.

EXAMPLE 12 crosslinking of ortho-UPR resins containing moieties of the formulae (IIa) and (IIb)

Such thermosets are represented by the formulae (IIa), (IIb), (III) and (V). To the unsaturated polyester resin obtained in example 11, styrene (stabilized with a radical inhibitor) was added in a weight ratio of 40:60, and additionally 4, N-trimethylaniline (0.08 wt%) and benzoyl peroxide (1.0 wt%) were added. The formulation was mechanically stirred to achieve complete mixing, poured into an aluminum pan, and cured at 50 ℃ for 24 hours to obtain duroplastic properties.

Example 13 Synthesis of a Meta UPR resin containing a moiety of formula (Ib) (prophetic)

Such polymers are represented by the formulae (Ib), (IV) and (V). A reaction vessel equipped with a reflux condenser and a nitrogen inlet was charged with isophthalic acid (1.0 eq), 1, 2-propanediol (2.1-x eq) and 3-methylpent-2-ene-1, 5-diol (x eq, x ═ 1.0, 2.1) and heated to 210 ℃ for the desired reaction time. The reaction mixture was allowed to cool to 170 ℃, the reaction continued for another desired period of time while maleic anhydride (1.2 equivalents) was added, and then cooled to room temperature after the addition of the free radical inhibitor.

Example 14-crosslinking of Meta UPR resin containing moiety of formula (Ib) (prophetic)

Such thermosets are represented by the formulae (Ib), (IV) and (V). To the unsaturated polyester resin obtained in example 13 was added styrene (stabilized with a radical inhibitor) in a weight ratio of 40:60, and additionally 4, N-trimethylaniline (0.08 wt%) and benzoyl peroxide (1.0 wt%). The formulation was mechanically stirred to achieve complete mixing, poured into a teflon mold, and cured at ambient conditions for 12h, and/or at an elevated temperature of 100 ℃ for 6 h.

Example 15 Synthesis of a Meta UPR resin containing moieties of formula (IIa) (prophetic)

Such polymers are represented by the formulae (IIa), (IV) and (V). A reaction vessel equipped with a reflux condenser and a nitrogen inlet was charged with isophthalic acid (1.0 eq), 1, 2-propanediol (2.1 eq) and 3-methylpent-2-enedioic acid (x eq, x ═ 0.6, 1.2) and heated to 210 ℃ for the desired reaction time. The reaction mixture was cooled to 170 ℃, the reaction continued for another desired period of time while maleic anhydride (1.2-x equivalents) was added, and then cooled to room temperature after the addition of the free radical inhibitor.

EXAMPLE 16 crosslinking of ortho-UPR resins containing moieties of formula (IIa) (prophetic)

Such a thermoset is represented by the formulae (IIa), (IV) and (V). To the unsaturated polyester resin obtained in example 15 was added styrene (stabilized with a radical inhibitor) in a weight ratio of 40:60, and additionally 4, N-trimethylaniline (0.08 wt%) and benzoyl peroxide (1.0 wt%). The formulation was mechanically stirred to achieve complete mixing, poured into a teflon mold, and cured at ambient conditions for 12h, and/or at an elevated temperature of 100 ℃ for 6 h.

Synthesis of polyurethane products

EXAMPLE 17 Synthesis of polyurethane containing formula (Id) with tin catalyst

Such polymers are represented by formulas (Id) and (XIIIE). To a solution of 0.250g of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide and 0.327g of 4,4' -methylenediphenyl diisocyanate in 5mL of dimethylacetamide was added 1 mole% dibutyltin dilaurate catalyst and the mixture was stirred at 80 ℃ for 5 hours under a nitrogen blanket. The reaction was quenched by precipitation into aqueous methanol (1:1 vol). The solid product was collected by filtration, washed with 50mL of methanol, and dried under vacuum at 70 ℃ for 24 h. (yield 90%; GPC (DMF, 70 ℃, vs. narrow PS standard): M_n＝963g mol^-1，M_w/M_n＝3.96；T_g＝92℃)。

EXAMPLE 18 Synthesis of polyurethane containing formula (Id) with acid catalyst

Such polymers are represented by formulas (Id) and (XIIIE). To a solution of 98mg of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide and 129mg of 4,4' -methylenediphenyl diisocyanate in 1mL of dimethylacetamide was added 1 mol% of p-toluenesulfonic acid catalyst, and the mixture was stirred under a nitrogen blanket for 24 hours. The reaction was quenched by precipitation into methanol. The solid product was collected by filtration, washed with 40mL of methanol, and dried under vacuum at 70 ℃ for 24 h. (yield: 82%; GPC (DMF, 70 ℃, vs narrow PS standard): M_n＝11,224g mol^-1，M_w/M_n＝3.70； T_g＝122℃)。

EXAMPLE 19 Synthesis of polyurethane #2 containing formula (Id) with tin catalyst

Such polymers are represented by formulas (Id) and (XIIIa). To a solution of 104mg of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide and 83. mu.L of hexamethylene diisocyanate in 1mL of dimethylacetamide was added 1 mole% dibutyltin dilaurate catalyst and the mixture was stirred under a blanket of nitrogen for 6 hours. The reaction was quenched by precipitation into methanol. The waxy product was collected by centrifugation, washed with 40mL of methanol and dried under vacuum at 70 ℃ for 24 h. (yield 80%; GPC (DMF, 70 ℃, vs narrow PS standard): M_n＝1,370g mol^-1，M_w/M_n＝4.38；T_g＝-7℃)。

EXAMPLE 20 formulation of vinyl carbamate (VU) resin

Such thermosets are represented by the formulae (Id) and (XIIIe). A mixture of 0.2g (2 eq) of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide (MVLea), 0.13g (2 eq) of (2-hydroxyethyl) methacrylate, 0.39g (3 eq) of 4,4' -methylenediphenyl diisocyanate, 0.5mL of styrene, 0.5mg of hydroquinone and 0.5. mu.L of dibutyltin dilaurate was stirred at 60 ℃ for 4 hours. After cooling to room temperature, the clear resin was accelerated by the addition of 4, N-trimethylaniline (0.08 wt%) and cured with benzoyl peroxide (1.0 wt%) at room temperature for 24 hours to give a hard clear solid.

EXAMPLE 21 formulation of vinyl carbamate (VU) resin

Such thermosets are represented by the formulae (Id) and (XIIIe). A mixture of 0.2g (2 equivalents) of 3, 5-dihydroxy-N- (2-hydroxyethyl) -3-methylpentanamide (MVLea), 0.13g (2 equivalents) of (2-hydroxyethyl) methacrylate, 0.39g (3 equivalents) of 4,4' -methylenediphenyl diisocyanate, 0.5mL of methyl acrylate, 0.5mg of hydroquinone and 0.5. mu.L of dibutyltin dilaurate was stirred at 60 ℃ for 4 hours. After cooling to room temperature, the clear resin was accelerated by the addition of 4, N-trimethylaniline (0.08 wt%) and cured with benzoyl peroxide (1.0 wt%) at room temperature for 24 hours to give a hard clear solid.

Synthesis of pendant MVL polyacrylates

Example 22 Synthesis of a polyacrylate containing formula (VIII)

Compound A (90mg) and azobisisobutyronitrile (3 mol%) were dissolved in 0.5mL of deoxygenated toluene and heated at 70 ℃ for 3h under a nitrogen blanket. The reaction was quenched by cooling to room temperature and the reaction vessel was opened to ambient air. The polymer suspension was precipitated from methanol, filtered, washed with 15mL of methanol and dried under vacuum at 70 ℃ for 24 h. (yield: 85%; GPC (DMF, 70 ℃, narrow contrast)PS standard): m_n＝17,372g mol^-1，M_w/M_n＝4.03)。

Example 23 Synthesis of a polyacrylate copolymer containing formula (VIII) (prophetic)

The procedure of example 12 was applied to a system comprising an equimolar mixture of compound a and (meth) acrylic acid, (meth) acrylamide or methyl (meth) acrylate.

EXAMPLE 24 Synthesis of a polyacrylate comprising formula (X) (prophetic)

A solution of the polymer from example 20 or 21 in a small volume of a suitable solvent (i.e., dimethylformamide) is cooled to 0 ℃ and mixed with a diamine (1 mole%, 5 mole%, 25 mole%, and/or 50 mole% per unit of compound a) (i.e., hexamethylenediamine) or lysine. After the allotted amount of time, unreacted reagents were removed by washing with the solvent employed, followed by washing with a low boiling point solvent (i.e., methanol), and the crosslinked polymer was then dried in vacuo.

Polyester/polyesterol synthesis

Example 25 Synthesis of polyester from MVL derived diol (prophetic)

Such polymers are represented by formula (Ib). A three-necked round-bottomed flask equipped with a vacuum adapter, nitrogen inlet and thermocouple was filled with 3.7g (25mmol) of dimethyl succinate, 1.2g (13mmol) of 1, 4-butanediol and 1.5g (13mmol) of 3-methylpent-2-ene-1, 5-diol. The mixture was bubbled with dry nitrogen for 0.5h and heated to 130 ℃. After 30 minutes, 0.1 mole% titanium (IV) tetraisopropoxide was added and the temperature was slowly raised to 180 ℃ under a continuous stream of nitrogen. After a further 3 hours, vacuum (0.1 mbar) was gradually applied and the temperature was raised to 210 ℃ for 2 h. The cooled mixture was dissolved in 40mL of chloroform and precipitated from 250mL of vigorously stirred methanol. The oily residue was purified by decanting off the methanol phase and washed with 3 x 200mL of methanol, followed by drying at high temperature in vacuo to constant weight. Yield: 1.2 g. GPC: m_n＝5,655g mol^-1，M_w/M_nCompare narrow PS standards in THF eluents ═ 3.22.

EXAMPLE 26 Synthesis of polyester from MVL derived diacid (prophetic)

Such polymers are represented by formula (IIb). A three-necked round-bottomed flask equipped with a distillation condenser, nitrogen inlet and thermocouple was filled with 6.0g (37mmol) of 3-hydroxy-3-methylglutaric acid and 3.4g (38 mmol) of butane-1, 4-diol, bubbled with dry nitrogen and heated to 130 ℃. After 30 minutes, 0.1 mole% titanium (IV) tetraisopropoxide was added and the temperature was slowly raised to 180 ℃ under a continuous stream of nitrogen. After a further 3 hours, vacuum (0.1 mbar) was gradually applied and the temperature was raised to 210 ℃ for 2 h. The cooled mixture was dissolved in 40mL of chloroform and precipitated from 250mL of vigorously stirred methanol. The white precipitate was filtered, washed with 3X 200mL of methanol, and dried under vacuum at elevated temperature overnight.

Example 27 Synthesis of polyester from MVlea

Such polymers are represented by formula (Id). In an oven dried one-necked flask, to a solution of 0.5g (2.6mmol) MVLea in 3mL anhydrous dimethylacetamide, 0.76mL anhydrous triethylamine (2.1 equivalents, 5.5mmol) was added and the reaction was cooled to 0 ℃. Adipoyl chloride (0.37mL, 0.9 eq) was added dropwise via syringe, causing a precipitate to form. The reaction mixture was stirred at the temperature for 4h, after which 5mL 0.5M HCl was added to quench the reaction, followed by 5mL dichloromethane. The phases were separated and the organic phase was further washed with 5mL of saturated ammonium chloride solution and 5mL of brine. The organic phase was dried over magnesium sulfate, filtered, and evaporated to yield 0.65 of polyester as a yellow oil. (GPC: M)_n＝1.852g mol^-1，M_w/M_n1.69, compare narrow PS standards in THF).

Example 28 Synthesis of 2,2' - ((((3-methylpent-2-en-1, 5-diyl) bis (oxy)) bis (methylene)) bis (ethylene oxide) (prophetic)

Such compounds are represented by formula (XVc). In a round-bottomed flask equipped with a reflux condenser were added 3.0g (26 mmol) of bio-based 3-methylpent-2-ene-1, 5-diol, 20mL of anhydrous dimethyl sulfoxide and 6.2g (110mmol) of KOH. To this mixture was slowly added 12.2mL (156mmol) of epichlorohydrin and the reaction was stirred at 50 ℃ for 16 h. After cooling back to room temperature, the mixture was filtered and the solvent was removed under reduced pressure. The residue was partitioned between saturated sodium chloride solution and diethyl ether. The product was purified by vacuum distillation.

(adapted from Crivello, J.V. "Design and Synthesis of multifunctional glycidyl ethers that undergo front-end polymerization" (journal of Polymer science A edition: Polymer chemistry (J.Polymer.Sci.A.Polymer.chem.)) 2006,44,6435-

EXAMPLE 29 Synthesis of 3-methyl-5- (oxiran-2-ylmethoxy) pent-2-enoic acid oxiran-2-ylmethyl ester (prophetic)

Such compounds are represented by formula (XVk). In a round bottom flask equipped with a reflux condenser was added 3.0g (45 mmol) of bio-based AML, 40mL of anhydrous dimethyl sulfoxide and 9.3g (165mmol) of KOH. To this mixture was slowly added 23.5mL (0.30mol) of epichlorohydrin and the reaction was stirred at 50 ℃ for 16 h. After cooling back to room temperature, the mixture was filtered and the solvent was removed under reduced pressure. The residue was partitioned between saturated sodium chloride solution and diethyl ether. The product was purified by vacuum distillation.

Example 30-3-methyl-1, 5-bis (ethyleneoxy) pent-2-ene (prophetic)

Such compounds are represented by formula (XVIb). The reactor was charged with 0.2mol of bio-based 3-methylpent-2-ene-1, 5-diol, NaOH (7 mol%) and CsF (7 mol%) and acetylene was supplied to reach an initial pressure of 10-14 atm. The reaction was carried out with stirring and heated to 135-140 ℃ for 15 h. After aeration, the reaction product was purified by distillation under reduced pressure.

An alternative method of vinyl ether synthesis can be found in winterheimer, d.j.; shade, r.e.; merlic, C.A. "Methods for Vinyl Ether Synthesis" (Synthesis) 2010,15, 2497-.

Example 31 Synthesis of polycarbonate (prophetic)

This polymer is represented by formula (XVIIb). The stirred reactor was charged with biobased 3-methylpent-2-ene-1, 5-diol (1mol) and diphenyl carbonate (1mol) and initially maintained at 20 mbar at 200 ℃. The temperature was slowly raised to 290 ℃ and 310 ℃ and the pressure was reduced to 0.1 mbar until the desired molecular weight was obtained.

EXAMPLE 32 Synthesis of 6-methyl-3, 7-dioxabicyclo [4.1.0] heptan-2-one (prophetic)

This compound is represented by formula (XXVI). To a solution of bio-based AML (6.7g) in methanol (50mL) was added 30% H over a period of 10 minutes at 0 deg.C₂O₂Aqueous solution (18.3 mL). Immediately followed by dropwise addition of 5N NaOH (0.4 mL). After stirring at about 10 ℃ until complete conversion was reached, the reaction was quenched with brine, extracted with dichloromethane and concentrated in vacuo. The crude product was purified by cougell distillation to yield the title compound as a clear colorless oil. (adapted from organic chemistry Communication (org. Lett.), 2012,14(5), p. 1322. 1325.)

It will be clear to those skilled in the art that the above compounds represent general monomers for ring-opening polymerisation, in particular with parallel or subsequent cross-linking capability for the manufacture of thermosets.

Example 33 Ring opening polymerization of Compound B (prophetic)

Compound B has been reported as a product of the photochemical [2+2] cycloaddition of acetylene to AML (1982, 104,5486-5489, J.Am.chem.Soc.).

To a stirred anhydrous solution of bio-based compound B (1.0 equivalent) and benzyl alcohol (0.01 equivalent) was added triazabicyclodecene (0.005 equivalent) and stirred at room temperature in a dry inert atmosphere until the target molecular weight was reached. The reaction was then quenched by the addition of benzoic acid (0.005 eq), dissolved in chloroform, precipitated from methanol, washed with methanol, and dried in vacuo. The resulting polymer is represented by formula (XXVII).

It will be clear to those skilled in the art that the above compounds represent general purpose monomers for ring opening polymerization, particularly with the ability to be concurrently or subsequently crosslinked for the manufacture of thermoset materials such as unsaturated polyester resins.

EXAMPLE 34 manufacture of mevalonolactone

The gene fragments encoding mvaE (acetyl-CoA acetyltransferase/HMG-CoA reductase, GenBank accession AAG02438) and mvaS (HMG-CoA synthetase, GenBank accession AAG02439) in enterococcus faecalis V583 were amplified from their genomic DNA (obtained from ATCC). These fragments were inserted into a vector (having a pBR322 origin backbone, ampicillin marker lacIq, rrnB transcriptional terminator sequence) under the control of IPTG inducible Trc promoter-lac operon to obtain plasmid pSE 1.

Plasmid pSE1 was used to pair XL-1Blue strain (end A1 gyrA96 (nal) using the procedure outlined in Sambrook-Maniatis (Green, M.R.; Sambrook, J., eds. (Molecular Cloning: A Laboratory Manual), fourth edition, 2002)^R)thi-1recA1 relA1 lac glnV44 F'[::Tn10 proAB⁺lacI^qΔ(lacZ)M15]hsdR17(rκ^-mκ⁺) ) was transformed to obtain the strain Escherichia coli-SE 1.

Escherichia coli-SE 1 strain was supplemented with 100. mu.g/l ampicillin in a 1-liter Erlenmeyer flaskPropagated in LB medium in 250mL of medium and incubated at 37 ℃ for 10 hours at 220rpm in an orbital shaker to an OD600 of 3. It was used as an inoculum for production in an Inforsen (Infors)5lt bioreactor. 1.75 l of production medium (containing 15g/l glucose, 7g/l KH)₂PO₄、1g/l NH₄Cl, 5g/l yeast extract, 1g/l citric acid, 10mg MnSO₄、2g/l MgSO₄、200mg/l FeSO₄And 10mg/l thiamine hydrochloride) was combined with 250mL inoculum in the bioreactor. With 20% NH₄OH maintains the pH at 7. The temperature was maintained at 32 ℃. Air was bubbled at 2 Liters Per Minute (LPM) and agitation was maintained at 700 rpm. After 10 hours of inoculation, 1ml of 1M IPTG was added to the bioreactor. An antifoaming agent is added as required. The glucose concentration was maintained at about 10g/l by adding 600g/l glucose solution to the bioreactor at 2 hour intervals. The bioreactor was stopped at 48 hours. The cells were separated from the culture broth by using a 0.45 microfilter to obtain a clear culture broth. It was found that at the end of the fermentation, the mevalonolactone concentration was 40 g/l.

Equivalents and incorporation by reference

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.

49页详细技术资料下载

Polymers prepared from mevalonolactone and derivatives

相关技术

网友询问留言